Manufacture of naphthylamine derivatives



Patented May 4, 1937 MANUFACTURE OF NAPHTHYLAMINE DERIVATIVES WilliamByres McKay,

Blackley, Manchester, 7

England, assignor to Imperial Chemical lindustries Limited, acorporation of Great Britain No Drawing. Application April 11, 1935,Serial No. 15,912. In Great Britain April 18, 1934 11 Claims.

This invention relates to an improved method of manufacturing acomposition of matter which is 1-hydrcxy-alkyl-amino-5-naphthel and/or1,5- di(hydroxy-alkyl-amino) naphthalene and which is useful in themanufacture of dyestuffs. This invention relates to an improvedmanufacture of l-hydroxy-alkyl-amino-5-naphthols (see British Patent No.410,843) and to the manufacture of new dyestuli intermediates.

It is an object of the invention to improve the method of manufacturingl-hydroxy-alkylamino-5-naphthol and/or l,5-di(hydroxy-alkylamino)naphthalene. Another object of the invention is to improve the method ofmaking the alkyl-amino derivatives of 1,5-dihydroxy-naphthalene. Anotherobject of the invention is to obtainnew and improved compositions ofmatter.

The objects of the invention are attained, generally speaking, byreacting 1,5-dihydroxy-naphthalene with primary hydroxy-alkyl-amine inthe presence of a water-soluble bisulfite in aqueous medium. The processof the invention is by causing reaction to take place between1,5-dihydroxy-naphthalene and a primary hydroxyalkyl-amine in presenceof an aqueous solution of a water-soluble bisulfite.

The products obtained are usuallya mixtur of the mono-and di-substitutedalkyl-amino derivatives of 1,5-dihydroxy-naphthalene. The productsobtained are l-hydroxy-alkyl-amino- 5-naphthols and1,5-di(hiydroxyialkyl amino) naphthalenes.

Whether one or the other product preponderates depends on the proportionof reagents used and the reaction conditions. If it is desired that thepreponderating derivative shall be l-hydroxy-alkyl-amino-5-naphthol,there should be in the reaction mixture a greater amount of1,5-dihydroxy-napthalene than of the primary hydroxy-aryl-amine. If anexcess of 1,5-di(hydroxy-alkyl-amino) naphthalene is desired in thefinal product, there should be a greater amount of the primaryhydroxy-aryl-amine than of the dihydroxy-naphthalene.

The following examples in which the parts are by weight, illustrate butdo not limit the invention.

Example 1 108 parts of aqueous paste containing 44% of1,5-dihydroxynaphthalene, 30 parts of ethanolamine, i. e.2-hydroxyethylamine, parts of a 40% aqueous solution of sodium bisulfiteand 200. parts of water are mixed together and either heated and stirredin a sealed vessel at 110- 115 C. for 5 hours or boiled and stirredunder reflux for 10 hours. 1000 parts of water are added to theresulting mixture and s-ufficient 40% aqueous sodium hydroxide solutionparts) to make it strongly alkaline to Clayton 5 yellow paper. Themixture is heated to boiling and cooled. 26 parts of1,5-di-(p-hydroxyethylamino) naphthalene crystallize out and arefiltered ofi. To the filtrate is added suflicient 36% hydrochloric acidparts) to make it strongly 10 acid to Congo red paper. It is thenfiltered. There is thus recovered a small amount of unchanged1,5-dihyclroxynaphthalene. Enough so dium carbonate is now added to thefiltrate to give a faintly alkaline reaction on brilliant yellow 15paper, when 21 parts of 1-(fi-hydroxyethylamino)-5-naphthol (35% yield)is precipitated.

This is filtered off, washed with a little water and dried.

The 30 parts of ethanolamine and 40 parts of 20 aqueous sodium bisulfitein the above example may be replaced by '70 parts of ethanolaminesulfite.

Example 2 314 parts of aqueous paste containing 38.3% 25 or1,5-dihydroxynaphthalene, 46 parts of 100% ethanolamine, i. e.Z-hydroxyethylamine, 195 parts of a 40% aqueous solution of sodiumbisulfite, 128 parts of 1,5-di-(p-hydroxyethylamino) -r1'aphthalene and113 parts of water are 30 mixed together and heated in a sealed vesselat -115 C. for 18 hours with agitation. 1500 parts of Water are added tothe resulting mixture and sufiicient 40% aqueous sodium hydroxidesolution (304 parts) to make it strongly alkaline 3 to Clayton yellowpaper. The mixture is heated to boiling and then cooled and filtered.The solid obtained is re-extracted with 750 parts of water containingsufiicient caustic soda to impart to the liquor an alkaline reaction toClayton 40 yellow paper and the mixture is again filtered. The-solidremaining consists of 130 parts of 1,5- di- (pi-hydroxyethylami-nod-.r1aphthalene-. To the united filtrates is added suflicient 36%hydrochloric acid (530 parts) to make it strongly acid to Congo redpaper. It is then filtered and the l,5-dioxynaphtha1ene thus recoveredis reextracted with 750 parts of water to which is added a littlehydrochloric acid. By filtration 50 there is thus recovered 32 parts ofunchanged 1.5-dihydroxynaphthalene. To the united filtrates is addedsufiicient sodium carbonate to give a faintly alkaline reaction onbrilliant yellow paper, when 88 gms. of l-p-hydroxyethylamino- 555-naphthol is precipitated. This is filtered, washed with a little waterand dried.

The 1,5-di-(hydroxyethylamino) naphthalene and unchanged1,5-dihydroxynaphthalene recov- 5 ered from the above example may againbe utilized for the purpose of carrying out the reaction of Example 1 orExample 2.

Other bisulfites than sodium bisulfite are useful. For instance,potassium bisulfite and calcium bisulfite alike are suitable and areexemplary of the utility which inheres in all watersoluble bisulfites.Other primary hydroxy-alkylamines can be substituted for the onespecifically disclosed in the above example. The specific temperaturewhich is recited should be taken as illustrative rather than limitativeof a range of temperatures since a wide range of temperatures will yieldresults of a kind.

As many apparently widely different embodiments of this invention may bemade Without departing from the spirit and scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsthereof except as defined in the appended claims. I claim:

1. The method of manufacturing a composition of matter which comprisesheating at 110-115 C. for five hours in a sealed vessel 108 parts of anaqueous paste containing 44% of 1,5-dihydroxynaphthalene, 30 parts ofZ-hydroxy-ethyl-amine, parts of a 40% solution of sodium bisulfite, and200 parts of water, diluting the reaction mass with 1000 parts of waterafter the heating, adding parts of a 40% solution of sodium hydroxide,boiling, cooling, and filtering, adding parts of a 36% solution ofhydrochloric acid, filtering, adding sodium carbonate in quantitiessufficient to give the solution a basic reaction under brilliant yellowpaper, and filtering off the reaction product.

2. The method of manufacturing a composition of matter which comprisesheating in confinement a mixture containing 1,5-dihydroxy-naphthalene,ethanolamine, a water-soluble bisulfite and water, after the reactiondiluting the reaction mass and boiling in the presence of an alkali,cooling, filtering, acidifying, filtering, making faintly basic, andfiltering oil the reaction product.

3. The method of manufacturing a composition of matter which comprisesreacting 1,5-dihydroxy-naphthalene and a primary hydroxy-alkylamine inthe presence of an aqueous solution of a water-soluble bisulfite.

4. A composition of matter comprising essentially1-hydroxy-alkyl-amino-5-naphthol, and 1,5-di(hydroxy-alkyl-amino)naphthalene.

5. A composition of matter comprising essentiallyl-hydroxy-alkyl-amino-5-naphthol, and 1,5-di(hydroxy-alkyl-amino)naphthalene, the 1- hydroxy-alkyl-amino-5-naphthol being present inpreponderating amount.

6. A composition of matter comprising essentiallyl-hydroxy-alkyl-amino-5-naphtho1, and 1,5-di(hydroxy-alkyl-amino)naphthalene, the 1,5-di(hydroxy-alkyl-amino) naphthalene being presentin preponderating amount.

'7. 1,5-di- (hydroxyalkylamino) -naphthalene.

8. 1,5-di- (hydroxyethylamino) -naphthalene.

9. The product identical with that produced by the process of claim 1.

10. The product identical with that produced by the process of claim 2.

11. The product produced by the process of claim 3.

WILLIAM BYRES McKAY.

CERTIFICATE OF CORRECTION. I

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